Heterometallic multinuclear nodes directing MOF electronic behavior

Ejegbavwo, Otega A.; Berseneva, Anna A.; Martin, Corey R.; Leith, Gabrielle A.; Pandey, Shubham; Brandt, Amy J.; Park, Kyoung Chul; Mathur, Abhijai; Farzandh, Sharfa; Klepov, Vladislav V.; Heiser, Brittany J.; Chandrashekhar, Mvs; Karakalos, Stavros G.; Smith, Mark D.; Phillpot, Simon R.; Garashchuk, Sophya; Chen, Donna A.; Shustova, Natalia B.

doi:10.1039/d0sc03053h

Title: Heterometallic multinuclear nodes directing MOF electronic behavior

Journal Article · 31 May 2020 · Chemical Science

DOI: https://doi.org/10.1039/d0sc03053h · OSTI ID:1635729

Ejegbavwo, Otega A. ^[1];

^[1]; Martin, Corey R. ^[1];

^[1]; Pandey, Shubham ^[2]; Brandt, Amy J. ^[1]; Park, Kyoung Chul ^[1]; Mathur, Abhijai ^[1]; Farzandh, Sharfa ^[1];

^[1]; Heiser, Brittany J. ^[1];

^[1];

^[2];

^[1];

^[1]

Univ. of South Carolina, Columbia, SC (United States)
Univ. of Florida, Gainesville, FL (United States)

Metal node engineering in combination with modularity, topological diversity, and porosity of metal-organic frameworks (MOFs) could advance energy and optoelectronic sectors. In this study, we focus on MOFs with multinuclear heterometallic nodes for establishing metal-property trends, i.e., connecting atomic scale changes with macroscopic material properties by utilization of inductively coupled plasma mass spectrometry, conductivity measurements, X-ray photoelectron and diffuse reflectance spectroscopies, and density functional theory calculations. The results of Bader charge analysis and studies employing the Voronoi–Dirichlet partition of crystal structures are also presented. As an example of frameworks with different nodal arrangements, we have chosen MOFs with mononuclear, binuclear, and pentanuclear nodes, primarily consisting of first-row transition metals, that are incorporated in HHTP-, BTC-, and NIP-systems, respectively (HHTP3- = triphenylene-2,3,6,7,10,11-hexaone; BTC3- = 1,3,5-benzenetricarboxylate; and NIP2- = 5-nitroisophthalate). Through probing framework electronic profiles, we demonstrate structure-property relationships, and also highlight the necessity for both comprehensive analysis of trends in metal properties, and novel avenues for preparation of heterometallic multinuclear isoreticular structures, which are critical components for on-demand tailoring of properties in heterometallic systems.

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Research Organization:: Univ. of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019360; SC0016574

OSTI ID:: 1635729

Alternate ID(s):: OSTI ID: 1681194; OSTI ID: 1776556

Journal Information:: Chemical Science, Vol. 11, Issue 28; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 11 works

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CCDC 2001459: Experimental Crystal Structure Determination A., Ejegbavwo, Otega; A., Berseneva, Anna; R., Martin, Corey https://doi.org/10.5517/ccdc.csd.cc255p68 The current record is supplemented by this dataset	dataset	January 2020
CCDC 2001460: Experimental Crystal Structure Determination A., Ejegbavwo, Otega; A., Berseneva, Anna; R., Martin, Corey https://doi.org/10.5517/ccdc.csd.cc255p79 The current record is supplemented by this dataset	dataset	January 2020
CCDC 2001461: Experimental Crystal Structure Determination A., Ejegbavwo, Otega; A., Berseneva, Anna; R., Martin, Corey https://doi.org/10.5517/ccdc.csd.cc255p8b The current record is supplemented by this dataset	dataset	January 2020
CCDC 2001462: Experimental Crystal Structure Determination A., Ejegbavwo, Otega; A., Berseneva, Anna; R., Martin, Corey https://doi.org/10.5517/ccdc.csd.cc255p9c The current record is supplemented by this dataset	dataset	January 2020
CCDC 2001463: Experimental Crystal Structure Determination A., Ejegbavwo, Otega; A., Berseneva, Anna; R., Martin, Corey https://doi.org/10.5517/ccdc.csd.cc255pbd The current record is supplemented by this dataset	dataset	January 2020
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